Modified melamine resins



United States Patent 3,194,71 MGDHFEED MELAMINE RESHNS James D. Larldu, West dpringrieid, and Gabriel M. Grudus, Springfield, Mass, assignors to Monsanto Company, a corporation of Delaware No Drawing. Filed May 7, 1963, Ser. No. 278,762 Claims. (Cl. 161-156) The present invention relates to novel thermosetting resins and to laminated structures prepared from the novel thermosetting resins.

Aminoplast type resins generally of the melamineformaldehyde type are widely employed in the preparation of laminated structures. While such resins have achieved great commercial success, the melamine-formaldehyde resins are subject to three well-recognized shortcomings. First, the laminating resins have poor stability in aqueous solutions in that the resin separates therefrom upon standing for relatively short periods of time, e.g., 1-2 days. The resin which separates from the solution cannot be redispersed and must be discarded. As a result of this fact, the manufacturers of melamine-formaldehyde laminating resins must separate these resins from the aqueous solutions in which they are prepared by spray-drying or analogous drying processes. This drying step adds substantially to the cost of the resins. Second, when melamine-formaldehyde resins are employed to impregnate the top or overlay sheet of decorative laminates, it is necessary to employ a special viscose rayon paper to obtain maximum transparency. Such viscose rayon papers are considerably more expensive than the high alpha cellulose paper employed in the print sheet of the decorative laminate. Third, laminates that are prepared from commercial melamine-formaldehyde laminating resins have poor postforming properties. It would be desirable to have available to the art melamine-formaldehyde type laminating resins which do not suffer from the above noted shortcomings.

It is an object of this invention to provide novel modi fied aminotriazine-aldehyde resins.

Another object of this invention is to provide aqueous solutions of modified aminotriazine-aldehyde resins which are stable over extended periods of time.

A further object of this invention is to provide decorative laminates in which the top or overlay sheet is a high alpha cellulose paper impregnated with a modified aminotriazine-aldehyde resin.

Yet another object of this invention is to provide a modified aminotriazine-aldehyde resin impregnated laminate having good postforrning properties.

Still other objects and advantages of this invention will be apparent from the following detailed description thereof.

The present invention provides novel resins which are the co-condensati-on products of an aminotriazine, an aldehyde and l,4-,3,6 sorbide which components are present in certain critical proportions.

The following examples are set forth to illustrate more clearly the principle and practice of this invention to those skilled in the art. Unless otherwise noted, where quantities are mentioned they are parts by Weight.

EXAMPLE I Part A ture for about 3 hours until the resin has a water-dilutability point of about The pH of the mixture'is Part B To illustrate the outstanding solution stability or the resin prepared in Part A above, a control resin solution is prepared by dissolving parts of a commercially-available melamine-formaldchyde laminating resin (formaldehyde/melamine rati-o=2.5/l) in 40 parts of water. The control resin solution is maintained at 25 C. and at the end of two days, the resin solution gelled.

EXAMPLE II A resin is prepared in exactly the same manner as described in Example I, Part A, except that in place of the melamine, a mixture is employed consisting of 90 parts of melamine and 10 parts of tetrahydrobenzoguanamine.

EXAMPLE III A resin is prepared in exactly the same manner as described in Example I, Part A, except that in place of the melamine, a mixture is employed consisting of 10 parts of melamine and 90 parts of tetrahydrobenzoguanamine.

EXAMPLE IV A resin is prepared from a mixture of 126 parts (1 mol) of melamine, 2-00 parts (2.5 mols) of 37% formalin solu tion, 50 parts of 1,4,3,6 sorbide and 1.0 part of thiourea following the procedure of Example I, Part A. The stability of an aqueous solution of the resin is comparable to the stability of the resin prepared in Example I, Part A.

EXAMPLE V Three decorative laminates designated as A, B, and C are prepared from 7 substrate sheets of krait paper impregnated with about 35 weight percent of a commercially available phenol-formaldehyde resin and suitable alphacellulosc print sheet and alpha-cellulose overlay sheet. Throughout this application, the stated percentages of resin, in a resin impregnated sheet, are based upon the weight of the final impregnated sheets. In addition to each of the resin solutions employed for preparing the laminates of this example, 0.5 Weight percent of the hydrochloric acid salt of Z-amino-Z-methyl propanoi-l based on the weight of the resin solids is added thereto. The catalyst aids in the curing of the laminate when subjected to heat and pressure. The laminates are prepared by pressing the assemblies for 20 minutes at 290 F. at a pressure of 1000 lbs. per square inch.

In each of the laminates prepared as described below, the print sheet is impregnated with about 4-0 weight percent with the resin employed and the overlay sheet with about Weight percent of the resin employed therein. In laminate A both the print sheet and the overlay sheet are impregnated With the resin of this invention which is described in Example I, Part A. In laminate B the overlay sheet is impregnated with the resin of this invention described in Example I, Part A, and the print sheet is impregnated with a commercially available melamine-formaldehyde resin having a formaldehy-de/ melamine mol ratio of 2.5/ 1. In laminate C both the overlay sheet and the print sheet are impregnated with a commercially available melamine-formaldehyde laminating resin having a formaldehyde/melamine moi ratio of 2.5 1.

The overlay sheets of decorative laminates A and B EXAMPLES/I A decorative laminate panel is prepared from 7 substrate sheets of kraft paper impregnated with about 35 Weight percent of a commercially available phenolformaldehyde resin and an alpha-cellulose print sheet carrying a dark Wood-grained pattern and impregnated with about 40 weight percent of a melamine-formaldehyde resin having a formaldehyde/melamine moi ratio of 2.5/1. One-half of the panel is overlaid with a 4-mil alpha-cellulose sheet impregnated with about 65 weight percent of the resin of this invention described in EX- arnple I, Part A. The other half of the panel is overlaid with a 4-mil sheet of viscose rayon paper impregnated with about 65 weight percent of the melamineformaldehyde resin employed to impregnate the print sheet. Witheach of the resin solutions employed in this example for preparing the laminates, 0.5 weight percent of the hydrochloric acid salt of 2-amino-2-methyl propanol-l based on the weight of the resin solids is added thereto. The laminate is pressed for minutes at 290 F, at a pressure of 1000 lbs. per square inch.

The section of the panel overlaid with the alphacellulose paper impregnated with the resin of this invention is as transparent as the section of the panel overlaid with the viscose rayon paper impregnated with the prior art melamine-formaldehyde resin. As a result, the section of the panel overlaid with the alpha-cellulose paper is as clear, as bright and as aesthetically pleasing as the section of the panel overlaid with the more expensive vis cose rayon paper.

Similar results are obtained when the alpha-cellulose overlay sheet is impregnated with a resin of Examples II, III or IV.

EXAMPLE VII Part A A postformable laminate is prepared from a postformable core, a print sheet, and an overlay sheet. The core consists of a bottom sheet of kraft paper, 3 intermediate sheets of crepe paper and a top sheet of kraft paper, all of said sheets being impregnated with about 35 weight percent of a commercially available postformable, phenol-formaldehyde resin. The print sheet is a 12-.rnil sheet of alpha-cellulose paper impregnated with 40 weight percent of the resin described in Example I, Palt A. The overlay sheet is a 4-mil sheet of alphacellulose paper impregnated with 65 weight percent of the resin described in Example I, Part A. As in Example VI, the same catalyst is employed with each of the resin solutions used in preparing the laminates and in the same amount. The laminate is prepared by pressing the assembly for 20 minutes at 275 F. at a pressure of 1000 lbs. per square inch. The finished laminate is about 0. 050 inch thick.

Part B A postformable laminate identical to that described in Part A above is prepared except that the print sheet and the overlay sheet are impregnated with the resin of Example II.

Part C A laminate identical to that described in Part A above is prepared except that the print sheet and the overlay sheet are impregnated with the resin of Example III.

Port D A control postformable laminate is prepared in exactly the same manner as described in Part A above except that the resin employed to impregnate the print sheet and the overlay sheet is a commercially available melamine-formaldehyde laminating resin havinga formaldehyde/melamine mol ratio of 25/1.

Part E The postformabili-ty of the laminates prepared in Parts A, B. C and D above is determined by NEMA method LP2-2.1'1. In this test method, the i laminates are heated and bent through an angle of in a series of jigs providing varying radii of curvature at the bend. The smaller the radius of curvaturethrough which the laminate can be bent without surface cracking the better is the postformabilityof the laminate. The laminates prepared in Parts A, B and C above with a resin of this invention can be bent through a /3 inch radius of curvature without cracking. By way of contrast, the laminate prepared in Part D above'with a prior art melamine-formaldehyde laminating resin cracks when bent through a radius of curvature of 1 inch.

As shown by'the examples set forth herein, the surprising discovery of the instant inventionis that the resin compositions employing the 1,4,3,6 sorbide are extremely stable and can be stored in aqueous solutions at 25 C. for periods of up to about 8 weeks without the resin precipitating therefrom. This is a substantial increase over the 1 or 2 days of stability obtained with a conventional resin of the melamine-formaldehyde type. In addition, the other surprising and important discovery is that when the resin composition of this invention is employed to impregnate a high alpha-cellulose paper that is subsequently used as the overlay sheet in the manufacture of a decorative laminate, the-resins of this invention provide superior transparency to that obtained with commercially available melamine formaldehyde resins. Further, in addition, another surprising discovery is that a decorative laminate prepared with resins of the instant invention has excellent postforming properties in comparison to decorative laminates employing only a melamine-formaldehyde resin.

The resinous thermosetting co-condensation products of this invention are characterized by the ratio of the reactants contained therein and comprise an aminotriazine, an aldehyde and 1,4,3,6 sorbide wherein the aldehyde is present in the ratio of 1.5-6.0 mols per mol of aminotriazine and the 1,4,3,6 sorbide' is present in an amount of 5-40 weight percent of the total resin. The 1,4,3,6 sorbide has the'formula:

wherein R is independently selected from the group consisting of an allryl radical having 1-4 carbon atoms and hydrogen. However, it should be noted that when at least three of the R groups are alkyl radicals of 3-4 carbon atoms each, the remaining R groups shouldbe hydrogen. If at least three of the R groups are alkyl radicals of 1-2 carbon atomseach, the remaining R groups may also be alkyl radicals of 1-2 carbon atoms each. The amount of 1,4,3,6 sorbide employed in the resin composition of this invention is 5-40 weight percent and, preferably, 15-25 weight percent of the resin composition. The preferred 'l,4,3,6 sorbide to be employed in the practice of this invention is where'the R groups of the above formula are all hydrogen.

Unless the limits of the 1,4,3,6' sorbide as'discussed in the paragraph above are carefully observed, the resins either will be deficient in certain important properties or will be relatively unstable in aqueous solution or both. If the resins contain less than 5 weight percent of the 1,4,3,6 sorbide, little or no improvement in resin properties is attained and resin solution stability is seriously hindered. On the other hand, if the resins contain more than about 40 weight percent of the 1,4,3,6 sorbide, the boiling water resistance of laminates prepared from such resins tends to be deficient. Optimum solution stability is attained when the resins contain about -25) weight percent of the sorbide, and optimum postformability is attained when the resins contain or more wei ht percent of the sorbide. An optimum balance of properties of transparency, solution stability and postformability is attained when the resins contain about 15- weight percent of the 1,4,3,6 sorbide.

in the practice of this invention, the aminotriazine compounds which are suitable for use herein are melamine, substituted melamines, or cycloaliphatic guanamines or mixtures of the above. The substituted melamines which can be employed herein are the alkyl melamines and aryl melamines which can be mono-, di-, trior tetra substituted. In the alkyl substituted melamines, each alkyl group can contain 1-6 carbon atoms and, preferably, 1-4 carbon atoms. Typical examples of some of the alltyl substituted melamines are monomethyl, melamine, dimethyl melamine, trimethyl melamine, monoethyl melamine and l-methyl-3-propyl-5-butyl melamine. In the aryl substituted melamines, each aryl group can contain l-2 phenyl radicals and, preferably, 1 phenyl radical. A typical example of an aryl substituted melamine is monophenyl melamine or diphenyl melamine.

The cycloaliphatic guanamines which can be employed in the practice of this invention can be any of the cycloaliphatic guanamines. Preferably, the cycloaliphatic guanamies should not have more than 15 carbon atoms. Typical examples of some of the cycloaliphatic guanamines are tetrahydrobenzoguanamine, hexahydrobenzoguanamine, 3-methyl-tetrahydrobenzoguanamine, 3-methylhexahydrobenzoguanamine, 3 ,4-dimethyl-l,2,5,6,-tetrahydrobenzoguanamine and 3,4-dimethylhexahydrobenzoguanarnine and mixtures thereof. A preferred cycloaliphatic guanamine is tetrahydrcbenzoguanamine.

It is sometimes desirable to employ a mixture of aminotriazine compounds such as melamine and an alkyl substituted melamine such as dimethyl melamine. Another mixture of aminotriazine compounds which has proved very successful as shown in the examples is a mixture of melamine and a cycloaliphatic guanamine such as tetrahydrobenzoguanamine. This mixture of aminotriazine compounds produced excellent results as shown in the examples. When employing a mixture of aminotriazine compounds as for example, melamine and tetrahydrobenzoguanamine, the mixture should consist of 95-5 weight percent of melamine and, correspondingly, 5-95 weight percent of tetrahydrobenzoguanamine. The same limits of the mixture would apply when using any mixture of the aminotriazine compounds. A preferred mixture is 75-95 weight percent of melamine and, correspondingly, 25-5 weight percent of tetrahydrobenzoguanamine.

The aldehyde employed in the practice of this invention can be any of the aliphatic aldehydes which condense with the aniinotriazine and the 1,4,3,6 sorbide. Particularly useful are acetaldehyde, butyraldehyde, formaldehyde, crotonic aldehyde, acrolein, heterocyclic aldehydes such as benzaldehyde, furfural and halogen substituted aldehydes such as alpha-chlor-obutyralde'hyde, alpha-fluorobutyraldehyde and the like. The mol ratio of aldehyde to aminotriazine should be 1.5-6.0 and, preferably, 2.0-4.0 mols per mol of aminotriazine. The preferred aldehyde to be employed in the practice of this invention is formaldehyde.

If desired, thiourea may be included in the resins of the invention in amounts of up to about 2.5 parts per 97.5 parts or" aminotriazine. The presence of this quantity of thiourea accelerates the cure rate of the resin and also increases the gloss of laminates prepared therefrom. In

addition, the presence of thiourea in the resin permits decorative laminates having an overlay sheet impregnated therewith to be removed from the press hot with little or no loss of gloss. In another embodiment of the invention, comparable results are obtained by admixing thiourea with .a solution of a resin of this invention in amounts of up to about 2.5 parts per 97.5 parts of the melamine contained in the resin.

When preparing resin compositions of this invention, the water-dilutability point of the resins can be critical with respect to the stability of solutions of the resins in water. For reasons which are not clearly understood, if the water-dilutability point is below 15% or above 35%, the resins precipitate from aqueous solutions in relatively short periods of time, e.g. 2-3 days and may even gel in the same short period of time.

When the resins of the invention are to be employed as laminating syrups, 40-60 wei ht percent of the resin should be dissolved in a corresponding 69-40 weight percent of a solvent consisting of either water or a mixture of a major amount of water and a minor amount of an acyclic alcohol containing 1-4 carbon atoms, e.g., methanol, ethanol, ethylene glycol, glycerine, propylene glycol, etc. The precise quantity of acyclic alcohol required in the water-alcohol solvent media will depend upon the specific structure or" the resin, but generally will be within the range of 0.5-40 weight percent and as a practical matter 0.5-20 weight percent and, preferably, less than 5 weight percent of the solvent media. Laminating syrups of the above type may be stored for periods of 6-8 weeks at temperatures in the range of 20-30 C. with little or no precipitation of the resin from the solution.

The reaction between the aminotriazine, l,4,3,6 sorbide and the aldehyde should be carried out at a pH of 7-11 and, preferably, at a pH of 8-10. The pH of the reaction mixture is conveniently adjusted with an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, triethanolamine, etc. The temperature of the reaction may be varied from about 60 C. to reflux tem perature at atmospheric pressure. For purposes of accurate control of reaction rate, and in order to control the properties of the reaction product, it is preferable to conduct the reaction at a temperature of about -100" C. for the greater part of the reaction time. In one embodiment of the invention, the l,4,3,6 sorbide and the aldehyde can be condensed in a neutral or slightly acidic aqueous medium. The pH is then adjusted to the alkaline side and the l,4,3,6 sorbide-aldehyde condensate is then reacted with the proper quantity of the aminotriazine to the desired water-dilutability oint.

Although this invention is primarily directed to a resin composition product wherein the l,4,3,6 sorbide is reacted with the aminotriazine and the aldehyde, equally excellent results in a laminate are obtained by adding the 1,4,3,6 sorbide to the laminating syrup, which laminating syrup has been previously described as to the preparation thereof. This is accomplished by first preparing a laminating syrup of an aminotriazine-aldehyde resin. To this, the 1,4,3,6 sorbide is then added in an amount to constitute 5-40 weight percent based on the weight of the resin solids employed. Again, the aminotriazine and the aidehyde can be any of those previously described and in the rnol ratios set forth herein. It is preferred, however, to react the 1,4,3,6 sorbide with the aminotriazine and the aldehyde since this will produce a more stable laminating syrup when employed as such for preparing decorative laminates. In addition, it will avoid the added step of mixing the 1,4,3,6 sorbide in the laminating syrup.

The preparation of laminates employing the resins of the invention in general follows procedures which are well-known in the art. Inert filler sheets of alpha-cellulose paper, viscose rayon paper, glass cloth or cloth prepared from cotton, wool or synthetic fibers are impregnated with 30-80 weight percent of the resin and dried to a volatile content of the order of 3-l0%. An assembly of such resin-impregnated sheets is then subjected to a pressure of the order of 100-2000 lbs. per square inch and heated for -60 minutes at a temperature of 20"- 400 F.

When preparing laminates employing the resins of this invention, it may be desirable to add a catalyst to the resin in order to aid in the curing process of the treated filler sheets. Common catalysts so employed are those catalysts which liberate acid when subjected to heat and are added in an amount varying from 0.1 weight percent to 10.0 weight percent based on the weight ofwthe resin solids and, preferably, will vary from 0.5 weight percent to 4.0 weight percent thereof. Such catalysts include the organic and inorganic acid salts of primary, secondary, and tertiary amines such. as the hydrochloric acid salt of Z-amino-Z-methyl propanol-l, the hydrochloric acid salt of mono-, diand tri-ethanolamine, the hydrochloric acid salt of Z-dimethylamino-Z-methyl propanol, the paratoluene sulfonic acid salt of aminomethyl propanol-l, the chloroacetic acid salt of pyridine, the tri-ammonium acid pyrophosphate salt of aminomethyl propanol-l, the phosphoric acid salt of 2-arnino-2-methyl propanol-l, the phosphoric acid salt of mono-, di-, and tri-ethanolamines, the phosphoric acid salt of Z-dimethylamino-Z-methyl propanol, ethylene sulfite, etc. Other catalysts include the inorganic salts of inorganic acids such as ammonium chloride, magnesium chloride, zinc chloride, etc. In fact, the catalyst system may includ-e mixtures of the above diflerent types of catalysts such as a mixture of magnesium chloride and the hydrochloric acid salt of 2-amino-2- methyl propanol-l, a mixture of the hydrochloric acid salt of monoethanolamine and diethanolamine, etc. The catalyst can be added to the kettle near the end of the condensation reaction or it may be added to the laminating syrup when used to prepare laminates.

Decorative laminates are prepared from an assembly of (1) a rigid substrate, (2) a resin-impregnated print sheet, i.e., a paper sheet having a design printed thereon, and (3) a resin-impregnated top or overlay sheet. In such decorative laminates, the rigid substrate may consist of any suitable material such as plywood, a resinbonded wood fiber board or the like, a plurality of resinimpregnated sheets, etc. The printed sheet preferably is impregnated with a resin of this invention, although in other embodiments of the invention the print sheet can be impregnated with an unmodified melamine-formaldehyde resin or a melamine-formaldehyde resin that is moditied with minor amounts of other compounds such as toluene sulfonamide or an omega cyanoalkylguanamine. The overlay sheet is impregnated with a resin of this invention. Although the overlay sheet may be viscose rayon paper, an outstanding feature of the inventionis that excellent transparency is obtained even when the overlay sheet is a high alpha-cellulose paper. This is a matter of considerable importance, since the viscose rayon papers presently employed in the overlay sheet are considerably more expensive than the high. alpha-cellulose papers which are employed as the print sheet. High alpha-cellulose papers are defined as those in which the fibrous web consists of at least weight percent of alpha-cellulose.

Where decorative laminates having postforming properties are desired, the rigid substrate must be of a postforrnable material such as a plurality of paper sheets (preferably creped) impregnated with specially formulated postformable varnished such as phenol-formaldehyde resins, cresol-phenol-formaldehyde resins, etc. The print sheet must be impregnated with either the resins of the present invention or another postformable aminoplast resins such. as a melamine-toluene sulfonamide-formaldehyde resin or a melamine-omega cyanoalkylguanamine-formaldehyde resin or mixtures of other known postfior-ma'ble aminoplast resins. The overlay sheet is impregnated with a resin composition of this invention.

The resinous condensation product of this invention can also be used in such other applications as the bonding of fibers to form fibrous structures which are used as oil filters, water filters, air filters, thermal insulation, molded iurniture parts, etc., as orthopedic resins, as the bonding of wood veneer to form laminate plywood structures and for high density molded objects which may or may n employe powdered-mica, asbestos, cellulosie fibers such as bleached alpha-cellulose flock, unbleached alpha-cellulose flock and may include pigments.

It will thus be seen that the objects set forth above, among those made apparent from the description, are efficiently attained, and since changes may be made in carrying out the above process and in the composition set forth without departing from the scope of this invention, it is intended that all matters contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

l. A resinous thermosetting co-condensation product comprising an aminotriazine, an aldehyde and l,4,3,6 sorbide having the formula:

wherein R is independently selected from the group consisting of 'hydrogenand an alkylradical having l-4 carbon atoms, providing that when at least three ofthe R groups have .alkyl radicals of 3-4 carbon atoms each, the remaining R groups shall be hydrogen; said aldehyde being presen-t in the ratio of 1.5-6.0 mols per mol of aminotriaz-ine; said 1,4,3,6 sorbide constituting 5-40 weight percent of the total reactants; said am-inot-riazine being selected from the group consisting of melamine, substitutedmelamines and cycloaliphatic guanamine, and mixtures thereof.

2. A resinous t-hermosetting co-condensation product of claim 1 wherein all of the R groups of the 1,4,-3,6 sorbide are hydrogen. and the l,4,3,6 sorbide constitutes 15-25 Weight percent of the total reactants.

3. The resinous thermosetting co-condensation pr duct of claim 1 wherein the aminotriazhie is a mixture of -5 weight percent of melamine and, correspondingly, 5-95 Weight percent of a cycloaliphatic g'uanamine.

4. Theresinous thermosetting co-condensation product of claim 3 wherein the cycloaliphatic .guanamine is -tetra hydrobenzoguanamine.

5. The resinous thermosetting co-condensation product of claim 3 wherein the aldehyde is formaldehyde.

6. The resinous thermosetting.co-condensation product of claim 1 wherein the aminotriazine is an alkyl substituted melamine containing up to'4 alkyl groups with each alkyl group containing 1-6 carbon atoms.

7. The resinous thermosetting co-condensation product of claim 2 wherein the aminotriazine is melamine and the aldehyde is formaldehyde. 7

3. A laminating syrup that is stable for an extended period of time and comprising 40-60 weight percent of the resinous thermosetting co-condensation product of claim 1 in solution in 60-40 weight percent of a solvent taken from the group consisting of water and mixtures of a major amount of Water and a minor amount of an acyclic .alcohol containing 1-4 carbon atoms.

9. The laminating syrup of claim 8 wherein the resinous thermosetting co-condensation product is that of claim'Z.

'10. The laminating syrup of'claim 8 wherein the resinous thermosetting co-condensation product is that of claim 3.

11.- The laminating syrup of-claim 8, having in solution therewith a catalyst which will liberate acid upon heating.

12. A normally rigid postformable laminate comprising a sheeted inert filler bonded with the thermoset res-in of claim 1.

13. A normally rigid pos-tformable laminate comprising a sheeted inert filler bonded with the thermoset resin of claim 2.

14. A normally rigid postformable laminate comprising a sheeted inert filler bonded with the thermoset resin of claim 3.

15. A decorative laminate comprising a t-hermoset resinbonded assembly of a rigid substrate, a decorative print sheet impregnated with a melamine-formaldehyde resin, and an overlay sheet impregnated with a resin of claim 1- 16. A decorative laminate as in claim 12 in which the "overlay sheet is a sheet of high alpha-cellulose paper impregnated with a resin of claim 1.

17. A process for preparing a laminating syrup which comprises mixing in a solvent solution a resinous thermosetting co-condensation product of an aminot-riazine and an aldehyde which reactants are in the ratio of 1.56.0 mols of the aldehyde per mol of aminot-riazine and 540 Weight percent based on the weight of the resin solids 1,4,3,6 sorbide having the formula:

wherein R is independently selected from the group consisting of hydrogen and an alkyl radical having 1-4 carbon atoms, providing that when at least three of the R groups have alkyl radicals of 3-4 carbon atoms each, the remaining R groups shall be hydrogen; said solvent being taken from the group consisting of water and mixtures of a major amount of Water and -a minor amount of an acyclic alcohol containing 1-4 carbon atoms; said aminotriazine being selected from the group consisting of melamine, substituted melamines and cycloaliphatic guanamine and mixtures thereof.

18. The process of claim 17 wherein the 1,4,3,6 sorbide constitutes 15- 25 weight percent based on the Weight of the resin solids.

19. The process of claim 17 wherein the aminotriazine is melamine and the aldehyde is formaldehyde.

20. The process of claim 17 wherein the aminotri-azine is a mixture of -5 Weight percent of melamine and, correspondingly, 5-95 weihgt percent of tetrahydrobenzoguanamine.

References Cited by the Examiner UNITED STATES PATENTS 2,773,788 12/56 Magrane et al. 161165 2,801,198 7/57 Morris et a1 161-263 3,082,180 3/6 3 Boldizar et al 260l7.3

ALEXANDER WYMAN, Primary Examiner.

MORRIS SUSSMAN, Examiner. 

1. A RESINOUS THERMOSETTING CO-CONDENSATION PRODUCT COMPRISING AN AMINOTRIAZINE, AND ALDEHYDE AND 1,4,3,6 SORBIDE HAVING THE FORMULA:
 15. A DECORATIVE LAMINATE COMPRISING A THERMOSET RESINBONDED ASSEMBLY OF A RIGID SUBSTRATE, A DECORATIVE PRINT SHEET IMPREGNATED WITH A MELAMINE-FORMALDEHYDE RESIN, AND AN OVERLAY SHEET IMPREGNATED WITH A RESIN OF CLAIM
 1. 